Products



Patented Mar. 12, 1946 PRODUCTS Jesse Harmon, Wilmington, Del, assignorto E. 1. (iii llont de Nemours & Company, Wilmington, Del., acorporation of Delaware No Drawing. Application February 22, 19%, SerialNo. 523,466

Claims.

This invention relates to new halogen-containing organic chemicalproducts and to a process for their preparation. More paticularly, thisinvention relates to the reaction of vinyl acetate with carbontetrachloride and to the products obtained therefrom.

It is known that when an unsaturated compound such as vinyl acetate istreated with a peroxygen catalyst, polymers are obtained. Furthermore,when a mixture of two or more unsaturated compounds, such as vinylacetate and vinyl chloride is subjected to polymerizing conditions inthe presence of a peroxygen catalyst, interpolymers are formed. Themacromolecules thus produced have physical properties which are ofgreater interest than their chemical properties. For example,such solidpolymers or interpolymers can be formed into fibres and films while thechemical properties are characteristic of the multiplicity of repeatinggroups present rather than reactivity of the molecule as a unit.However, it has not previously been discovered that vinyl acetate can beconverted into liquid products of relatively low molecular weight bytreatment under suitable conditions with carbon tetrachloride.

An object of this invention is the production of compounds which arerepresented by the general formula 0 ClzF-CHzCH-J-Cl in which n is aninteger. Further objects will appear from the description givenhereinafter.

These objects are accomplished by the following invention whichcomprises reacting vinyl acetate with carbon tetrachloride preferably inthe presence of a compound which is a catalyst for the polymerization ofvinyl acetate and a non-catalyst for the Friedel-Crafts reaction.

The novel reaction products obtained by this invention can berepresented by the general formula where n is an integer and in generalhas a value of from 1 to approximately 8. When n in the above formula isunity, the compound is a simple addition product of carbon tetrachlorideto vinyl acetate. However, where the value of n is greater than unity,the compounds are not simple addition products. For simplicity, theselatter compounds have been called "telomers" and the process for theirproduction has been termed telomerization. The designation telomer" isderived from the Greek te1os" meaning end and the Greek "mer meaningpart. Telomers differ from simple compounds or polymers in that the endgroups of the chain formed from the vinyl compound are characteristic.They difier from polymers or interpolymers in that they have a lowermolecular weight and in chemical and physical properties. They areusually liquids or semi-liquids. The broader aspect of telomeriza tionis more completely described in pending application Serial No. 438,466filed April 10, 19%2.

The reaction between carbon tetrachloride and vinyl acetate can becarried out at any temperature between room temperature (25 C.) andapproximately 150 C. to produce the 1:1 addition product and liquidproducts having a plurality of vinyl acetate units and ends from onemolecule of carbon tetrachloride. A ratio of vinyl acetate to carbontetrachloride of between 10 to 3 and 1 to 10 parts by weight is employedin this reaction. The reaction is preferably carried out in the presenceof from 0.01 to 5% (based on the weight of vinyl acetate) of apolymerization catalyst, such as benzoyl peroxide, which is efiectivefor the polymerization of vinyl acetate and ineffective as aFriedel-Crafts catalyst. By Friedel-Crafts catalysts are meant suchcompounds as aluminum chloride or boron trifluoride as used inalkylation or acetylation reactions as described in Chemical Reviews 17,327-392 935) The catalysts operable in the present invention have beendesignated telomerization catalysts in Hanford and Joyce copendingapplication, Serial No. 438,466, filed April 10, 1942. The time for thereaction of carbon tetrachloride with vinyl acetate is not critical,being dependent upon temperature, catalyst and the presence of an inertdiluent such as benzene or isooctane.

When temperatures of approximately to autogenous pressure developed, oreven higher pressures that may be employed.

In the preferred procedure, the reaction is stopped when the major partof the low boiling vinyl acetate and carbon tetrachloride reactants havebeen used and the products are concentrated by vaporization of thevolatile unreadted carbon tetrachloride and vinyl acetate. product isnot a single molecular species but is a mixture ofstructurallyhomologous compounds differing from one another by thenumber of vinyl The reaction and -769 parts of carbon tetrachloride.

acetate units which comprise the chain between the chlorine and CCl:groups. For many applications, the mixture can be employed per seinasmuch as it is a mixture of functionally similar compounds of varyingchain length. Furthermore, where the average number of vinyl acetateunits present is large, for example, three to eight, the compounds aresubject to decomposition when heated and it is, therefore, undesirableto subject such a mixture to distillation. However, the addition productof carbon tetrachloride to vinyl acetate and the lower molecular weightproducts, such as those having two or three vinyl acetate units can bedistilled at reduced pressure. Products having more than eight vinylacetate units tend to be solid.

This invention is further illustrated but not limited by the followingexample in which the parts given are by weight.

Example Into a reaction vessel equipped with a reflux condenser wereplaced 172 parts of vinyl acetate After refluxing for a few minutes, 0.3part of benzoyl peroxide was added, after which the temperature of theboiling mixture gradually rose from 73 to 84 C. over a period of tenhours. No additional rise in temperature 'was noted when a similaradditional amount of catalyst was added. After distillation ofunreactedvinyl acetate and carbon tetrachloride by heating on a waterbath at a pressure of 20 centimeters of mercury (absolute), a total of336 parts of a colorless, oily liquid re-- mained; When this liquid wassubjected to vacuum distillation, two principal fractions 'wereobtained. The first fraction boiled at 62.5 C. at 0.9 millimeter andunderwent no decomposition upon standingfor several weeks. This materialwas found to contain 59.3% chlorine. The calculated value for thechlorine content of the 1 to 1 addition product of vinyl acetate tocarbon tetrachloride, (CC13(CH2CHOCOCH3)CD is 59.1%.

The higher boiling product, which had a boiling point of 107. C. at 1.5mm. pressure, had a chlorine content of 43.0%. The calculated chlorinecontent of a compound having two vinyl acetate units combined with onecarbon tetrachloride unit (CC1sCH'2CI-I(OCOCH3)CH2CH(OCOCH3)C1) is42.2%. Attempted distillation of higher boiling products present in thereaction product, even under diminished pressure, is accompanied by somedecomposition.

The 1:1 addition compounds and the products having a plurality of vinylacetate units and ends from one molecule of carbon tetrachloride whichare obtained from vinyl acetate and carbon tetrachloride by therpresentnovel reaction react with aldehyde reagents such as phenylhydrazine andsemicarbazide hydrochloride, indicating that the products formed arealpha-chloroesters of acetic acid. For example, the semibarbazone of the1 to 1 addition product of vinyl acetate and carbon tetrachloride wasfound to darken at 160 C. and melt with decomposition at 192 C.(uncorrected); it contained 19.3% nitrogen as determined by the Dumasmethod. The calculated nitrogen content of the compound is 19.3%. A2,4-dinitrophenylhydrazone i was readily prepared and found to melt at173 C. (uncorrected) when heated at a rate of 10 C. per minute. Theanalysis for this hydrazone was: I l:l6.4% (Dumas); calculated for Thereaction products obtained from carbon tetrachloride and vinyl acetatehave chlorine which is capable of replacement or further reaction bychemical ragents, for example, halogen can be removed by treatment witha methanolic solution'of hydrogen chloride followed by treatmentwithconcentrated aqueous alkali.

As catalysts which are useful in the promotion of this reaction, therecan be used any catalyst effective for the polymerization of vinylacetate and ineffective in the Friedel-Crafts reaction. Useful catalystsinclude compounds having directly linked oxygen atoms, e. g., peroxygencompounds such as diacyl peroxides such as benzoyl peroxide, propionylperoxide, lauroyl peroxide; dialkyl peroxides such as diethyl peroxide;other peroxides such as ascaridol, cyclohexanone peroxide, diethylperdicarbonate hydrogen peroxide. tertiary butyl hydroperoxide, ozone,ozonides, etc. as trimethylamine oxide; ultra-violet light in thepresence of photo sensitizers such as diacetyl. mercury, alkyl iodidesand acetone; and metal alkyls. Especially useful when the reaction iscarried out in an aqueous emulsion are water soluble persulfates,perborates, and percarbonates, for example, sodium, potassium, orammonium persulfate, perborate, or percarbonate. Emulsifying agentsand/or a buffer may be employed with a persulfate or a similar catalystwhen an aqueous system is used. Furthermore, oxidizable sulfoxycompounds such as bisulfite may be advantageously employed inconjunction with a persulfate or similar catalyst in aqueous systems. Itis to be understood that carbon tetrachloride and vinyl acetate canreact to form the addition product and products of low molecular weightwhen no catalyst is present, however, the reaction requires a longerperiod of time. For this reason, the addition of small amounts of acatalyst of the type hereinbefore mentioned is advantageous.

The compounds obtained by the process of this invention are useful asplasticizers, solvents, and in other applications. For many such uses,separation of the individual compounds is unnecessary in view. of thefact that the compounds all have the same functional groups and differonly in the number of'vinyl acetate units present. By virtue of thepresence of active halogen in the 1:1

, addition product and products having a plurality of vinyl acetateunits and ends from one molecule of carbon tetrachloride produced inthis reaction, hydrolysis or other chemical reactions convert thesecompounds to other materials having further utility for specialapplications. Thus, hydrolysis gives rise to polyhydroxy compoundsuseful in resin or coating compositions.

The above description and examples are intended to be illustrative only.Any modification of, or variation therefrom, which conforms to thespirit of the invention, is intended to be included within the scope ofthe claims.

What is claimed is:

1. A liquid mixture of compounds of the formula wherein n is an integerfrom one to eight.

Other catalysts include amine oxides such momma 3 2. A liquid having thegeneral formula 4. A process of obtaining polychlorinated chchcmcaflnmcompounds which comprises reacting at 25450 C. vinyl acetate with from0.3 to 10 parts, per part cmco" of vinyl acetate, of carbontetrachloride. wherein n is an integer from one to eight. 5 I 5. Processof claim 4 wherein a. peroxy poly- 3. A liquid of the formula.merlzatlon catalyst is employed.

ChCCHxCHC1O-COCH5 JESSE HARMONY.

